CN114107960B - SnO preparation by using stannous oxalate as raw material2Method for forming electron transport layer film - Google Patents
SnO preparation by using stannous oxalate as raw material2Method for forming electron transport layer film Download PDFInfo
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- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002834 transmittance Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 3
- 238000004528 spin coating Methods 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 12
- 239000010409 thin film Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CCGSUNCLSOWKJO-UHFFFAOYSA-N cimetidine Chemical compound N#CNC(=N/C)\NCCSCC1=NC=N[C]1C CCGSUNCLSOWKJO-UHFFFAOYSA-N 0.000 description 1
- 229960001380 cimetidine Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the technical field of optoelectronic materials and devices, and relates to a method for preparing a SnO 2 electron transport layer film by taking stannous oxalate as a raw material, which comprises the following steps: respectively placing the transparent conductive substrate into deionized water and alcohol for ultrasonic cleaning, and then placing the transparent conductive substrate into an oven for drying; dissolving stannous oxalate in a hydrogen peroxide solution, carrying out ultrasonic treatment on the solution, and filtering to obtain a SnO 2 precursor solution with the concentration of 0.25-1 mol/L; and coating the SnO 2 precursor solution on a transparent conductive substrate, and heating at 100-250 ℃ for 30min to obtain the high-light-transmittance SnO 2 electron transport layer film. The photoelectric conversion efficiency of the perovskite battery obtained by adopting the SnO 2 film prepared by the invention can reach more than 20 percent, and the perovskite battery prepared by using the commercial SnO 2 nano particles under the same conditions is superior to the perovskite battery.
Description
Technical Field
The invention belongs to the technical field of optoelectronic materials and devices, and relates to a method for preparing a SnO 2 electron transport layer film by taking stannous oxalate as a raw material.
Background
The perovskite solar cell has the characteristics of low cost and high efficiency. Currently, the authentication efficiency of perovskite solar cells has reached 25.5%, which can be compared with commercial crystalline silicon solar cells, and the perovskite solar cells have great commercial application potential. Perovskite solar cells are typically composed of an electron transport layer, a perovskite layer, a hole transport layer, and an electrode, wherein the electrode comprises a transparent conductive electrode and a metal electrode.
For perovskite solar cells of positive type structure, the most commonly used electron transport layers typically include TiO 2,SnO2 and ZnO. Compared with TiO 2 and ZnO, the SnO 2 material has higher electron mobility, higher optical transmittance, more suitable energy band position and excellent chemical stability, so that the SnO 2 electron transport layer is more and more important. The raw material for preparing the SnO 2 electron transport layer is typically SnCl 2、SnCl4、SnCl2·2H2O、SnCl4·5H2 O and commercial SnO 2 nanoparticle solutions. The SnO 2 electron transport layer (publication No. CN 104157788A) can be prepared by using the sol formed by the hydrolysis of SnCl 2·2H2 O, but the hydrolysis process has poor controllability and is easy to be influenced by external environment. SnCl 2·2H2 O is dissolved in absolute ethyl alcohol, snO 2 nano particles can be obtained after heating reflux and long-time aging, and the highest photoelectric conversion efficiency of the perovskite battery based on the SnO 2 electron transport layer prepared by the method can reach 19.20％(Qingshun Dong,Yantao Shi,Chunyang Zhang,Yukun Wu,Liduo Wang,Energetically favored formation of SnO2 nanocrystals as electron transfer layer in perovskite solar cells with high efficiency exceeding 19％,Nano Energy,2017)., but the method is complex to operate and takes longer time. The commercial SnO 2 nano particles are used as an electron transport layer, and the perovskite solar cell (Qi Jiang,Zema Chu,Pengyang Wang,Xiaolei Yang,Heng Liu,Ye Wang,Zhigang Yin,Jinliang Wu,Xingwang Zhang,Jingbi You,Advanced Materials,2017). with high efficiency and high stability can be prepared, but the commercial SnO 2 nano particle solution has higher cost and unknown chemical composition, and is not beneficial to further optimizing the performance of the perovskite solar cell. In conclusion, the research on the SnO 2 electron transport layer which is low in cost, simple to operate and controllable in chemical composition has important significance for further reducing the manufacturing cost of the perovskite battery and improving the photoelectric conversion efficiency of the perovskite battery.
Disclosure of Invention
The invention aims to provide a method for preparing a SnO 2 electron transport layer film by taking stannous oxalate as a raw material, wherein the photoelectric conversion efficiency of a perovskite battery prepared by adopting the SnO 2 film can reach more than 20 percent, and the method is superior to that of a perovskite battery prepared by using commercial SnO 2 nano particles under the same condition.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a method for preparing a SnO 2 electron transport layer film by taking stannous oxalate as a raw material, which comprises the following steps:
s1, respectively placing a transparent conductive substrate into deionized water and alcohol for ultrasonic cleaning, and then placing the transparent conductive substrate into an oven for drying;
S2, dissolving stannous oxalate in a hydrogen peroxide solution, carrying out ultrasonic treatment on the solution, and filtering to obtain SnO 2 precursor solution with the concentration of 0.25-1 mol/L;
S3, coating the SnO 2 precursor solution on a transparent conductive substrate, and heating at 100-250 ℃ for 30min to obtain the high-light-transmittance SnO 2 electron transport layer film.
Preferably, the concentration of the hydrogen peroxide solution is 30%.
Preferably, the heating temperature in step 3 is 180 ℃.
Preferably, the coating in step 3 is performed by spin coating, spray coating or printing.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, stannous oxalate is taken as a raw material, and heat is released when the stannous oxalate is dissolved into hydrogen peroxide, so that the dissolution of the stannous oxalate is accelerated, the whole process is completed within a short period of minutes, and the preparation process is simple, and compared with the preparation by taking SnCl 2·2H2 O as a raw material, the preparation time is greatly shortened; compared with the commercial SnO 2 nano-particles used as the electron transport layer, the cost is greatly reduced.
The invention takes stannous oxalate as raw material, only generates carbon dioxide and water in the reaction process, does not generate other toxic and harmful substances, and has the characteristics of environmental protection.
The photoelectric conversion efficiency of the perovskite battery obtained by adopting the SnO 2 film prepared by the invention can reach more than 20 percent, and the perovskite battery prepared by using the commercial SnO 2 nano particles under the same conditions is superior to the perovskite battery.
Drawings
FIG. 1 is an X-ray photoelectron spectrum of a SnO 2 film prepared in example 1 of the present invention.
FIG. 2 is an ultraviolet-visible transmittance spectrum of the SnO 2 film prepared in example 2 of the present invention.
FIG. 3 is an SEM image of a thin film of SnO 2 prepared from various amounts of stannous oxalate according to example 2 of the present invention.
Fig. 4 is a statistical chart of open circuit voltage, short circuit current density, filling factor and photoelectric conversion efficiency of perovskite batteries prepared by using SnO 2 films prepared by using different amounts of stannous oxalate according to example 3 of the present invention.
Fig. 5 is a graph showing a statistical comparison of the photoelectric conversion efficiency of different perovskite cells in example 4 of the present invention, wherein Reference represents a commercial SnO 2 electron transport layer and Sn75 represents a SnO 2 electron transport layer prepared from stannous oxalate.
Fig. 6 is a plot of optimum current density versus voltage for different perovskite cells in example 4 of the invention. Wherein Reference represents a commercial SnO 2 electron transport layer and Sn75 represents a SnO 2 electron transport layer made of stannous oxalate.
FIG. 7 is an SEM image of a SnO 2 film at different heating temperatures according to example 5 of the present invention.
Detailed Description
The following examples are illustrative of the present invention and are not intended to limit the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. The test methods in the following examples are conventional methods unless otherwise specified.
Example 1
1) The silicon wafer is cut into square blocks of 1cm multiplied by 1cm, then sequentially washed by deionized water and alcohol in an ultrasonic manner, and finally heated and dried in an oven at 80 ℃.
2) 155Mg of stannous oxalate is weighed, 1mL of hydrogen peroxide with the concentration of 30% is added, ultrasonic treatment is carried out for 15min, and transparent and clear SnO 2 precursor solution with the concentration of 0.5mol/L is obtained after filtration.
3) Spin-coating the solution on a cleaned silicon wafer substrate. Spin coating conditions were 3000rpm,30s. And then heating at 180 ℃ for 30min to obtain the SnO 2 film.
The composition analysis of the prepared SnO 2 film was performed using XPS, as shown in fig. 1. As can be seen from fig. 1, the main components of the thin film are Sn and O elements, and the content of C element is very low, which indicates that the SnO 2 thin film can be successfully prepared by the method.
Example 2
1) The FTO conductive glass is cut into square blocks with the length of 2cm multiplied by 2cm, then the square blocks are sequentially ultrasonically cleaned by deionized water and alcohol, and finally the square blocks are heated and dried in an oven at the temperature of 80 ℃.
2) 51.7Mg, 103.4mg, 155mg and 206.7mg of stannous oxalate are respectively weighed, added into 1mL of 30% hydrogen peroxide solution, and subjected to ultrasonic treatment for 15min after the stannous oxalate is completely dissolved, and transparent and clear SnO 2 precursor solutions with the concentration of 0.25mol/L, 0.5mol/L, 0.75mol/L and 0.1mol/L are obtained after filtration.
3) The SnO 2 precursor solution is spin-coated onto the FTO conductive glass substrate at 4000rpm for 30s. And then heating at 180 ℃ for 30min to obtain the SnO 2 film.
The transmittance of the SnO 2 film was measured using an ultraviolet-visible spectrometer and the result is shown in fig. 2. As can be seen from fig. 2, the SnO 2 film has a higher transmittance than the original FTO glass after being covered with a layer of SnO 2.
As a result of observing the surface morphology of the SnO 2 film by SEM, the stannous oxalate contents in FIGS. 3-a to 3-d were 0.25mol/L, 0.5mol/L, 0.75mol/L and 0.1mol/L, respectively, as shown in FIG. 3. As can be seen from FIG. 3, when the mass of stannous oxalate was gradually increased from 51.7mg to 206.7mg, the grain boundaries of the FTO film became progressively blurred, indicating that the surface of the FTO grains was covered with a dense SnO 2 film.
Example 3
Perovskite thin films were prepared using SnO 2 thin films prepared in example 2 at stannous oxalate masses of 51.7mg, 103.4mg, 155mg, and 206.7mg, respectively.
1) The SnO 2 film was treated under uv-ozone atmosphere for 5min, and then a perovskite light absorbing layer was prepared on the SnO 2 film. Spin-coating 1.3mol/L PbI 2 solution on a SnO 2 film substrate, and heating at 70 ℃ for 1min; after it was cooled to room temperature, an organic salt solution (60 mg of cimetidine (FAI), 6mg of methylamine chloride (MACl), 6m of methylamine bromide (MABr) was spin-coated on the PbI 2 film and dissolved in 1mL of isopropyl alcohol solution), followed by heating at 150 ℃ for 15min.
2) And preparing a Spiro-OMeTAD hole transport layer. 72.3mg of Spiro-OMeTAD, 17.5. Mu.L of lithium salt (520 mg of lithium bistrifluoromethane sulfonimide (Li-TFSI) dissolved in 1mL of acetonitrile), 28.5. Mu.L of tBP dissolved in 1mL of chlorobenzene, and then spin-coated onto the surface of the perovskite thin film.
3) And preparing a metal Ag electrode. And (3) evaporating a layer of Ag electrode on the surface of the Spiro-OMeTAD hole transport layer by using a vacuum thermal evaporation device.
4) The performance of the perovskite cell was tested under standard AM1.5 simulated solar light, and the results are shown in fig. 4. The performance of each group of 25 batteries was counted and the average results are shown in table 1.
TABLE 1 perovskite cell Performance test results prepared with different stannous oxalate amounts
Example 4
Commercial SnO 2 aqueous solution was diluted in a volume ratio of 1:5 to give commercial SnO 2 precursor solution, and a perovskite battery was produced with reference to example 3.
The performance of 40 perovskite cells prepared with commercial SnO 2 and stannous oxalate masses of 155mg was counted: when using stannous oxalate to prepare the SnO 2 electron transport layer, the average open circuit voltage of the battery is 1.092V, the short circuit current density is 24.15mA cm -2, the filling factor is 77.91%, and the photoelectric conversion efficiency is 20.54%; when a commercial SnO 2 electron transport layer was used, the cell had an average open circuit voltage of 1.072V, a short circuit current density of 24.18mAcm -2, a fill factor of 75.72% and a photoelectric conversion efficiency of 19.61%.
It can be seen that the perovskite cell performance of the SnO 2 electron transport layer prepared using stannous oxalate is superior to the commercial SnO 2 electron transport layer.
Example 5
155Mg of stannous oxalate was weighed and spin-coated to obtain a SnO 2 film by the procedure of example 2. The heating temperature in step 3) was set to 100 ℃, 180 ℃ and 250 ℃, respectively. After heating for 30min, the surface morphology of the SnO 2 film was observed using SEM, as shown in FIG. 7, wherein the heating temperatures of FIGS. 7-a to 7-c were 100 ℃, 180 ℃ and 250 ℃, respectively. As can be seen in fig. 7, the SnO 2 film was able to completely cover the underlying FTO when heated at 100 ℃ and 180 ℃; when the temperature is raised to 250 ℃, small amounts of holes appear in the SnO 2 film.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and other embodiments can be easily made by those skilled in the art through substitution or modification according to the technical disclosure in the present specification, so that all changes and modifications made in the principle of the present invention shall be included in the scope of the present invention.
Claims (2)
1. The method for preparing the SnO 2 electron transport layer film by taking stannous oxalate as a raw material is characterized by comprising the following steps:
s1, respectively placing a transparent conductive substrate into deionized water and alcohol for ultrasonic cleaning, and then placing the transparent conductive substrate into an oven for drying;
S2, stannous oxalate is dissolved in a hydrogen peroxide solution, and the solution is subjected to ultrasonic treatment and filtration to obtain SnO 2 precursor solution with the concentration of 0.25-1 mol/L; the concentration of the hydrogen peroxide solution is 30%;
S3, coating the SnO 2 precursor solution on a transparent conductive substrate, and heating at 180 ℃ for 30min to obtain the high-light-transmittance SnO 2 electron transport layer film.
2. The method according to claim 1, wherein the coating in step 3 is performed by spin coating, spray coating or printing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111233565.0A CN114107960B (en) | 2021-10-22 | 2021-10-22 | SnO preparation by using stannous oxalate as raw material2Method for forming electron transport layer film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4924017A (en) * | 1987-08-05 | 1990-05-08 | Japan Exlan Company Limited | Stannic acid anhydride |
| RU1809846C (en) * | 1990-07-18 | 1993-04-15 | Минское производственное объединение "Калибр" | Solution for preparing of semiconducting films on tin dioxide-base |
| CN111628080A (en) * | 2019-02-28 | 2020-09-04 | 北京宏泰创新科技有限公司 | Perovskite solar cell and preparation method of perovskite absorption layer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4924017A (en) * | 1987-08-05 | 1990-05-08 | Japan Exlan Company Limited | Stannic acid anhydride |
| RU1809846C (en) * | 1990-07-18 | 1993-04-15 | Минское производственное объединение "Калибр" | Solution for preparing of semiconducting films on tin dioxide-base |
| CN111628080A (en) * | 2019-02-28 | 2020-09-04 | 北京宏泰创新科技有限公司 | Perovskite solar cell and preparation method of perovskite absorption layer |
Non-Patent Citations (2)
| Title |
|---|
| Bifunctional SnO2 Colloid Offers No Annealing Effect Compact Layer and Mesoporous Scaffold for Efficient Perovskite Solar Cells;Liangbin Xiong等;Advanced functional materials;2103949 * |
| Organic-free synthesis of nanostructured SnO2 thin films by chemical solution deposition;Aleksej Zarkova等;Thin Solid Films;第649卷;219-224 * |
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